WO2019044019A1 - 多層膜及び二液硬化型コーティング剤 - Google Patents

多層膜及び二液硬化型コーティング剤 Download PDF

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WO2019044019A1
WO2019044019A1 PCT/JP2018/013911 JP2018013911W WO2019044019A1 WO 2019044019 A1 WO2019044019 A1 WO 2019044019A1 JP 2018013911 W JP2018013911 W JP 2018013911W WO 2019044019 A1 WO2019044019 A1 WO 2019044019A1
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Prior art keywords
meth
polyol
protective layer
surface protective
mass
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PCT/JP2018/013911
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English (en)
French (fr)
Japanese (ja)
Inventor
雅雄 木口
伸行 松岡
亮一 中井
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ハリマ化成株式会社
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Application filed by ハリマ化成株式会社 filed Critical ハリマ化成株式会社
Priority to KR1020207002389A priority Critical patent/KR102555048B1/ko
Priority to PCT/JP2018/031789 priority patent/WO2019044843A1/ja
Priority to US16/642,420 priority patent/US20200254743A1/en
Priority to CN201880048913.7A priority patent/CN110945096B/zh
Priority to JP2019539540A priority patent/JP7208903B2/ja
Priority to TW107130475A priority patent/TWI791600B/zh
Publication of WO2019044019A1 publication Critical patent/WO2019044019A1/ja

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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • B05D2252/10—Applying the material on both sides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2503/00—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to a multilayer film having a surface protective layer excellent in watermark resistance and scratch resistance, and a two-component curable coating agent for forming the surface protective layer.
  • Such surface treatment is performed by applying a surface protective layer to the article surface.
  • a surface protective layer for example, (1) a method of forming a surface protective layer by applying a two-component curing type coating agent to the surface of an article, and (2) a multilayer film having a surface protective layer and an adhesive layer And the like.
  • Example 1 of Patent Document 1 a surface protective layer containing a polyurethane obtained by reacting 100 parts of a (meth) acrylic polymer having a hydroxyl value of 45 mg KOH and 28.07 parts of an isocyanate crosslinking agent, a substrate layer, and An adhesive sheet having an adhesive layer is disclosed.
  • Water may adhere to the surface-treated article as droplets due to rainfall or washing, which may cause stains generally called "water marks".
  • the water mark is a phenomenon in which the attached water evaporates and the mineral component contained in the water precipitates and remains as a white mark. Water marks reduce the appearance of the article surface. Therefore, the surface protective layer is required to improve the water-mark resistance.
  • the surface of the surface-treated article may be damaged due to contact or collision of flying objects such as pebbles and dust, and the appearance may be deteriorated. Therefore, the surface protective layer is also required to have excellent scratch resistance.
  • An object of the present invention is to provide a multilayer film having a surface protective layer which is excellent in watermark resistance and scratch resistance, and a two-component curable coating agent for forming the surface protective layer.
  • the multilayer film of the present invention is A substrate layer, Polyol (P) and polyisocyanate (I) having a hydroxyl value of 25 to 380 mg KOH / g and a fluorine atom content of 0.01 to 20% by mass, which are integrally laminated on the first surface of the substrate layer.
  • a surface protection layer comprising polyurethane, which is a reaction product with And a pressure-sensitive adhesive layer laminated and integrated on the second surface of the base material layer.
  • the multilayer film of the present invention includes a surface protective layer laminated and integrated on the first surface of the substrate layer.
  • the surface protective layer contains a polyurethane which is a reaction product of a polyol (P) having a hydroxyl value of 25 to 380 mg KOH / g and a fluorine atom content of 0.01 to 20% by mass and polyisocyanate (I).
  • P polyol
  • I polyisocyanate
  • the 1st surface and 2nd surface of a base material layer mean the surface which has the largest area of a base material layer.
  • Polyol (P) In the present invention, using a polyol (P) having a hydroxyl value of 25 to 380 mg KOH / g, a polyurethane obtained by reacting this polyol (P) with a polyisocyanate (I) is contained in the surface protective layer.
  • the urethane bond contained in the polyurethane can impart appropriate hydrophilicity to the surface protective layer surface.
  • the moisture attached to the surface protective layer can spread on the surface of the surface protective layer to make it difficult to form droplets, and the watermark resistance of the surface protective layer can be improved. Therefore, it is possible to reduce the occurrence of stains called "water marks" due to the moisture attached to the surface protective layer.
  • the concentration of the mineral component contained in the water per unit area of the surface protective layer surface can be reduced by spreading the water adhering to the surface protective layer with time to reduce the contact angle, It is possible to reduce the deposition of mineral components as white marks (ie, "water marks") on the surface protective layer after the evaporation of Such an effect can be evaluated based on, for example, the "rate of change of contact angle" in the evaluation of the watermark resistance in the examples described later. The rate of change of the contact angle is evaluated to what extent the contact angle of the water droplet has decreased 300 seconds after the water droplet is attached to the surface protective layer.
  • the surface protective layer has an appropriate degree of repulsion immediately after water comes in contact with the surface of the surface protective layer.
  • Water-based hereinafter, also simply referred to as "initial water repellant”
  • the initial water repellency can be evaluated based on, for example, the “initial contact angle” in the evaluation of the watermark resistance in the examples described later. As the “initial contact angle” is higher, it means that the surface protective layer exhibits high water repellency immediately after water comes in contact with the surface of the surface protective layer.
  • the watermark resistance of the surface protective layer can be comprehensively evaluated on the basis of both the "rate of change of contact angle" and the “initial contact angle” in the evaluation of the watermark resistance in Examples. Among them, it is the "rate of change of contact angle” that largely contributes to the watermark resistance. Therefore, the surface protective layer (A 1 ) having a large change rate in contact angle and a low initial contact angle has a smaller overall change rate in contact angle than the surface protective layer (A 2 ) having a high initial contact angle. Tend to be excellent in water mark resistance.
  • the application of the multilayer film to the surface of the article is carried out by pressing and sliding a squeegee (strap) on the surface protective layer after the multilayer film is placed on the surface of the article.
  • a squeegee trap
  • the hydrophilicity of the surface protective layer is simply improved in order to improve the water mark resistance of the surface protective layer, the squeegee slipperiness of the surface protective layer may be lowered. did. In such a case, the squeegee does not slip on the surface protective layer, causing sticking and causing damage to the surface protective layer.
  • the watermark resistance and the squeegee slippage sometimes conflict with each other, and when one is improved, the other may be decreased.
  • the surface protective layer is provided with excellent squeegee slipperiness while suppressing the decrease in the watermark resistance. It was possible to do. Thereby, it is possible to provide a surface protection layer which is excellent in both the watermark resistance and the squeegee slip resistance.
  • a polyurethane obtained by reacting a polyol (P) having a hydroxyl value of 25 to 380 mg KOH / g and a fluorine atom content of 0.01 to 20% by mass with a polyisocyanate (I) By using it, it is also possible to improve the scratch resistance of the surface protective layer. As a result, even if flying objects such as pebbles and dust come into contact with or collide with the surface protective layer, the appearance of the surface protection layer can be maintained while reducing the occurrence of scratches.
  • the multilayer film in order to attach the multilayer film to the surface of the article, after the multilayer film is placed on the article surface, the squeegee is pressed and slid on the surface protective layer. Tension is applied. However, the multilayer film can not withstand the pulling force of the squeegee and may cut.
  • a polyol (P) having a hydroxyl value of 25 to 380 mg KOH / g and a fluorine atom content of 0.01 to 20 mass% in the surface protective layer is reacted with polyisocyanate (I).
  • P polyol
  • I polyisocyanate
  • the hydroxyl value of the polyol (P) is 25 mg KOH / g or more, preferably 45 mg KOH / g or more, more preferably 70 mg KOH / g or more, and still more preferably 110 mg KOH / g or more.
  • the hydroxyl value of the polyol (P) is 380 mg KOH / g or less, preferably 340 mg KOH / g or less, more preferably 300 mg KOH / g or less, still more preferably 220 mg KOH / g or less, particularly preferably 150 mg KOH / g or less.
  • the polyol (P) having a hydroxyl value within the above range By using the polyol (P) having a hydroxyl value within the above range, a polyurethane containing a urethane bond in an appropriate amount can be formed, whereby the water mark resistance of the surface protective layer can be improved. . If the hydroxyl value of the polyol (P) is too high, the water repellency (initial water repellency) of the surface protective layer may be reduced, and a large amount of water may be deposited as droplets on the surface protective layer. It can be a source of watermarks. Furthermore, when the hydroxyl value of the polyol (P) is too high, the squeegee sliding property of the surface protective layer and the extensibility of the multilayer film may be deteriorated.
  • the hydroxyl value of the polyol (P) refers to the hydroxyl value of the solid content.
  • content of the fluorine atom of polyol (P) is 0.01 mass% or more, 0.03 mass% or more is preferable, 0.08 mass% or more is more preferable, 0.2 mass% or more is more preferable .
  • content of the fluorine atom of polyol (P) is 20 mass% or less, 19 mass% or less is preferable, 18 mass% or less is more preferable, 12 mass% or less is more preferable, 5 mass% or less Most preferred.
  • the fluorine atom contained in the polyol (P) can improve the water repellency (initial water repellency) and the squeegee slipperiness of the surface protective layer, but the fluorine atom reduces the hydrophilicity of the surface protective layer.
  • the watermark resistance may reduce the watermark resistance.
  • the content of the fluorine atom of the polyol (P) within the above range, it becomes possible to impart excellent squeegee slipperiness to the surface protective layer while suppressing the decrease in the watermark resistance. If the content of fluorine atoms in the polyol (P) is too low, the initial water repellency of the surface protective layer may be reduced, and a large amount of water may be deposited as droplets on the surface protective layer, which means that It may cause the occurrence of marks. Furthermore, when the content of fluorine atoms in the polyol (P) is too low, the squeegee slip resistance and scratch resistance of the surface protective layer may be reduced. Moreover, when content of the fluorine atom of polyol (P) is too high, the water
  • the polyol (P) preferably has no aromatic ring in the molecule. According to the polyol (P) having no aromatic ring in the molecule, it is possible to impart excellent weatherability to the surface protective layer. This can reduce yellowing of the surface protective layer over time.
  • the polyol (P) preferably contains a (meth) acrylic polyol.
  • the (meth) acrylic polyol is a (meth) acrylic polymer obtained by reacting a (meth) acrylic monomer and having a hydroxyl group at the terminal or side chain.
  • the (meth) acrylic polyol can be obtained using a conventional method for producing an acrylic polymer in the presence of a radical polymerization initiator. By using a (meth) acrylic polyol, both the watermark resistance and the squeegee slipperiness of the surface protective layer can be improved.
  • (meth) acryl means an acryl or methacryl.
  • the (meth) acrylate mentioned later means an acrylate or a methacrylate.
  • the (meth) acrylic polyol a polymer of a (meth) acrylic monomer containing a fluorine-containing (meth) acrylic monomer (a1) and a hydroxyl group-containing (meth) acrylic monomer (a2) is preferable.
  • a polymer of a (meth) acrylic monomer containing a fluorine-containing (meth) acrylic monomer (a1) and a hydroxyl group-containing (meth) acrylic monomer (a2) is preferable.
  • the fluorine-containing (meth) acrylic monomer (a1) preferably has a fluorine atom in the side chain, and more preferably a fluorine atom is not directly bonded to a carbon atom constituting the main chain.
  • Preferred examples of the fluorine-containing (meth) acrylic monomer (a1) include (meth) acrylic monomers represented by the following formula (1).
  • CH 2 C (R 1 ) -COO- (CH 2 ) n -Rf 1 (1)
  • R 1 is a hydrogen atom or a methyl group
  • n is an integer of 0 to 10
  • R f 1 is an alkyl group having 1 to 20 carbon atoms and a hydrogen atom of an alkyl group At least one of which is a fluoroalkyl group substituted with a fluorine atom
  • the fluoroalkyl group represented by Rf 1 in the formula (1) may be linear or branched.
  • the carbon number of the fluoroalkyl group is preferably 1 to 20, and more preferably 3 to 18.
  • the alkyl group for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- Decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-icosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, neopentyl group, t-pentyl group And n- (2-ethy
  • the fluoroalkyl group at least one of the hydrogen atoms of the alkyl group is substituted with a fluorine atom, but it is preferable that all hydrogen atoms bonded to primary carbon atoms be substituted with a fluorine atom, and the alkyl group is More preferably, all of the hydrogen atoms of are substituted by fluorine atoms.
  • fluorine-containing (meth) acrylic monomer (a1) trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) Acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, hexafluoro-2-propyl (meth) acrylate, heptafluoro-2-propyl acrylate, etc. Can be mentioned.
  • 2- (perfluorohexyl) ethyl (meth) acrylate is preferable, and 2- (perfluorohexyl) ethyl acrylate is more preferable.
  • the fluorine-containing (meth) acrylic monomer (a1) may be used alone or in combination of two or more.
  • the content of the fluorine-containing (meth) acrylic monomer (a1) in the (meth) acrylic monomer is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and still more preferably 0.9% by mass or more preferable.
  • 50 mass% or less is preferable, as for content of the fluorine-containing (meth) acrylic monomer (a1) in a (meth) acrylic monomer, 40 mass% or less is more preferable, 20 mass% or less is more preferable, and 3 mass % Or less is particularly preferred.
  • the content of the fluorine-containing (meth) acrylic monomer (a1) is too low, the initial water repellency of the surface protective layer may be reduced, and the watermark resistance may be reduced.
  • the content of the fluorine-containing (meth) acrylic monomer (a1) is too low, the squeegee slip resistance and scratch resistance of the surface protective layer may be reduced.
  • content of a fluorine-containing (meth) acrylic-type monomer (a1) is too high, the water
  • Examples of the hydroxyl group-containing (meth) acrylic monomer (a2) include (meth) acrylic acid alkyl esters containing a hydroxyl group.
  • a hydroxyl-containing (meth) acrylic monomer (a2) for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (meth) acrylate and the like .
  • 2-hydroxyethyl (meth) acrylate is preferable.
  • the hydroxyl group-containing (meth) acrylic monomer (a2) may be used alone or in combination of two or more.
  • the content of the hydroxyl group-containing (meth) acrylic monomer (a2) in the (meth) acrylic monomer is preferably 4% by mass or more, more preferably 10% by mass or more, and still more preferably 22% by mass or more.
  • 90 mass% or less is preferable, as for content of the hydroxyl-containing (meth) acrylic monomer (a2) in a (meth) acrylic monomer, 82 mass% or less is more preferable, and 60 mass% or less is more preferable.
  • the content of the hydroxyl group-containing (meth) acrylic monomer (a2) is too low, the water adhering to the surface protective layer may not be able to be spread over time, and the watermark resistance may be lowered.
  • the scratch resistance of the surface protective layer may be lowered.
  • the content of the hydroxyl group-containing (meth) acrylic monomer (a2) is too low, the scratch resistance of the surface protective layer may be lowered.
  • the content of the hydroxyl group-containing (meth) acrylic monomer (a2) is too high, the initial water repellency of the surface protective layer may be reduced, and the watermark resistance may be reduced.
  • the content of the hydroxyl group-containing (meth) acrylic monomer (a2) is too high, the squeegee slipperiness of the surface protective layer may be reduced.
  • (Meth) acrylic monomer mass ratio of fluorine-containing (meth) acrylic monomer (a1) to hydroxyl-containing (meth) acrylic monomer (a2) [mass of fluorine-containing (meth) acrylic monomer (a1) / hydroxyl group 0.003 or more is preferable, 0.020 or more is more preferable, 0.025 or more is further more preferable, 0.030 or more is especially preferable, and, as for the mass of the contained (meth) acrylic monomer (a2), 0.033 or more Is most preferred.
  • the mass ratio [(a1) / (a2)] is too low, the squeegee slip resistance and the watermark resistance of the surface protective layer may be reduced.
  • the mass ratio of the fluorine-containing (meth) acrylic monomer (a1) to the hydroxyl group-containing (meth) acrylic monomer (a2) [mass of the fluorine-containing (meth) acrylic monomer (a1)
  • the mass of the / hydroxy group-containing (meth) acrylic monomer (a2)] is preferably 7.5 or less, more preferably 5 or less, still more preferably 2 or less, particularly preferably 1 or less, and most preferably 0.12 or less. If the mass ratio [(a1) / (a2)] is too high, the watermark resistance of the surface protective layer may be reduced.
  • the (meth) acrylic monomer used for the polymerization of the (meth) acrylic polyol preferably contains a siloxane bond-containing (meth) acrylic monomer (a3). That is, as the (meth) acrylic polyol, a fluorine-containing (meth) acrylic monomer (a1), a hydroxyl group-containing (meth) acrylic monomer (a2), and a siloxane bond-containing (meth) acrylic monomer (a3) The polymer of the (meth) acrylic-type monomer containing is preferable. By using the siloxane bond-containing (meth) acrylic monomer (a3), excellent squeegee slipperiness can be imparted to the surface protective layer.
  • siloxane bond containing (meth) acrylic-type monomer (a3) the monomer shown by following formula (2) or (3) is mentioned preferably.
  • R 2 is an alkyl group having 1 to 12 carbon atoms
  • R 3 is an alkylene group having 1 to 10 carbon atoms
  • R 4 is a hydrogen atom or a methyl group
  • p represents an integer of 2 to 150.
  • R 5 and R 8 each represent a hydrogen atom or a methyl group
  • R 6 and R 7 each represent an alkylene group having 1 to 10 carbon atoms
  • q represents an integer of 2 to 150
  • alkyl group represented by R 2 examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group.
  • 1-10 are preferable and, as for carbon number of the alkylene group shown by R 3 in Formula (2), 1-5 are more preferable.
  • the alkylene group represented by R 3 include a methylene group, an ethylene group, an n-propylene group, and an n-butylene group.
  • each alkylene group represented by R 6 and R 7 include, for example, a methylene group, an ethylene group, an n-propylene group, and an n-butylene group.
  • siloxane bond-containing (meth) acrylic monomer (a3) examples include ⁇ -butyl- ⁇ - (3-methacryloxypropyl) polydimethylsiloxane, ⁇ -mono (methacryloxymethyl) polydimethylsiloxane, and ⁇ And ⁇ -di (methacryloxymethyl) polydimethylsiloxane and the like. Among them, ⁇ -butyl- ⁇ - (3-methacryloxypropyl) polydimethylsiloxane is preferable.
  • the siloxane bond-containing (meth) acrylic monomer (a3) may be used alone or in combination of two or more.
  • the content of the siloxane bond-containing (meth) acrylic monomer (a3) in the (meth) acrylic monomer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 5% by mass or more. Mass% or more is particularly preferable.
  • the content of the siloxane bond-containing (meth) acrylic monomer (a3) in the (meth) acrylic monomer is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.
  • the (meth) acrylic monomers used for the polymerization of (meth) acrylic polyols include the above-mentioned fluorine-containing (meth) acrylic monomers (a1), hydroxyl group-containing (meth) acrylic monomers (a2), and siloxane bond-containing (meth) ) Other (meth) acrylic monomers other than acrylic monomers (a3) may be contained.
  • the (meth) acrylic-type monomer As another (meth) acrylic-type monomer, the (meth) acrylic-type monomer (a4) which does not contain a fluorine, a hydroxyl group, and a siloxane bond is mentioned.
  • (meth) acrylic-type monomer (a4) which does not contain a fluorine, a hydroxyl group, and a siloxane bond the (meth) acrylic-acid alkylester which does not contain a fluorine, a hydroxyl group, and a siloxane bond is mentioned, for example.
  • methyl (meth) acrylate, butyl (meth) acrylate and isobornyl (meth) acrylate are preferable, and methyl methacrylate, butyl acrylate and isobornyl methacrylate are more preferable.
  • the (meth) acrylic monomer (a4) containing no fluorine, hydroxyl group and siloxane bond may be used alone or in combination of two or more.
  • the content of the (meth) acrylic monomer (a4) not containing fluorine, hydroxyl group and siloxane bond is preferably 10% by mass or more, and more preferably 15% by mass or more.
  • the content of the (meth) acrylic monomer (a4) containing no fluorine, hydroxyl group and siloxane bond is preferably 95% by mass or less, more preferably 90% by mass or less.
  • 0.1 mass% or more is preferable, as for content of the (meth) acryl polyol in polyol (P), 10 mass% or more is more preferable, and 20 mass% or more is more preferable.
  • 90 mass% or less is preferable, as for content of the (meth) acryl polyol in polyol (P), 80 mass% or less is more preferable, and 65 mass% or less is more preferable.
  • the polyol (P) may contain other polyols in addition to the (meth) acrylic polyols described above.
  • Other polyols include polyether polyols, polyester polyols, and polycarbonate polyols. By using these polyols, the scratch resistance of the surface protective layer and the extensibility of the multilayer film can be improved.
  • the other polyols may be used alone or in combination of two or more.
  • polyether polyol As polyether polyol, aliphatic polyether polyol, alicyclic polyether polyol, etc. are mentioned.
  • aliphatic polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, pentaerythritol, dipentaerythritol, trimethylolpropane and trimethylolpropane.
  • Examples of the ionic polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bis (chloromethyl) oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene Oxides, styrene oxide, epichlorohydrin, glycidyl ether, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, benzoic acid glycidyl ester, etc.
  • Cyclic ethers are mentioned. Specific combinations of the two or more ionically polymerizable cyclic compounds include tetrahydrofuran and ethylene oxide, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, ethylene oxide and propylene oxide, butene-1- Examples include oxides and ethylene oxide, tetrahydrofuran and butene-1-oxide, ethylene oxide and the like.
  • Examples of the alicyclic polyether polyol include alkylene oxide adduct diol of hydrogenated bisphenol A, alkylene oxide adduct diol of hydrogenated bisphenol F, alkylene oxide adduct diol of 1,4-cyclohexanediol, and the like.
  • polyether polyol aliphatic polyether polyol is preferable and polytetramethylene glycol is more preferable.
  • 0.1 mass% or more is preferable, as for content of the polyether polyol in polyol (P), 10 mass% or more is more preferable, and 30 mass% or more is more preferable.
  • 90 mass% or less is preferable, as for content of the polyether polyol in polyol (P), 80 mass% or less is more preferable, and 70 mass% or less is more preferable.
  • polyester polyols examples include polycondensates obtained by reacting low molecular weight polyols with polybasic acids under known conditions.
  • the low molecular weight polyol includes a compound having two or more hydroxyl groups and having a number average molecular weight of less than 400, preferably less than 300.
  • the low molecular weight polyol for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3 -Or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene,
  • polybasic acids examples include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid , Azelaic acid, sebacic acid and other saturated aliphatic dicarboxylic acids (C11-13) such as maleic acid, fumaric acid, itaconic acid and other unsaturated aliphatic dicarboxylic acids such as orthophthalic acid, isophthalic acid and terephthalic acid , Toluenedicarboxylic acid, naphthalenedicarboxylic acid, other aromatic dicarboxylic acids such as hexahydrophthalic acid, other alicyclic dicarboxylic acids such as dimer acids, hydrogenated dimer acids, other carboxylic acids such as hetic acid, And acid anhydrides derived from these carboxylic acids, such as anhydrous oxa
  • polyester polyol for example, poly can be obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone, ⁇ -valerolactone, etc., using the above-mentioned low molecular weight polyol (preferably a dihydric alcohol) as an initiator.
  • lactones such as ⁇ -caprolactone, ⁇ -valerolactone, etc.
  • lactone polyester polyol obtained by copolymerizing the above-mentioned dihydric alcohol.
  • polyester polyol lactone type polyester polyol and polycaprolactone polyol are preferable, and polycaprolactone triol is more preferable.
  • 0.1 mass% or more is preferable, as for content of the polyester polyol in a polyol (P), 10 mass% or more is more preferable, and 30 mass% or more is more preferable.
  • 90 mass% or less is preferable, as for content of the polyester polyol in polyol (P), 80 mass% or less is more preferable, and 70 mass% or less is more preferable.
  • polycarbonate polyol for example, a ring-opening polymer of ethylene carbonate having the above-mentioned low molecular weight polyol (preferably, a dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5-pentanediol,
  • a dihydric alcohol for example, 1,4-butanediol, 1,5-pentanediol
  • An amorphous polycarbonate polyol obtained by copolymerizing a ring-opening polymer with a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol may, for example, be mentioned.
  • polycarbonate polyols include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, poly (tetramethylene / hexamethylene) carbonate diol, and poly [cyclohexylene bis (methylene) / hexamethylene] ] Carbonate diol etc. are mentioned.
  • the poly (tetramethylene / hexamethylene) carbonate diol is a copolymer of 1,4-butanediol, 1,6-hexanediol and dialkyl carbonate.
  • poly [cyclohexylene bis (methylene) / hexamethylene] carbonate diol is a copolymer of 1,4-cyclohexanedimethanol and 1,6-hexanediol with dialkyl carbonate.
  • poly [cyclohexylene bis (methylene) / hexamethylene] carbonate diol is preferably mentioned.
  • examples of commercially available products of poly [cyclohexylene bis (methylene) / hexamethylene] carbonate diol include Etanacol (registered trademark) UM-90 manufactured by Ube Industries, Ltd.
  • 0.1 mass% or more is preferable, as for content of the polycarbonate polyol in a polyol (P), 10 mass% or more is more preferable, and 30 mass% or more is more preferable.
  • 90 mass% or less is preferable, as for content of the polycarbonate polyol in polyol (P), 80 mass% or less is more preferable, and 70 mass% or less is more preferable.
  • (meth) acrylic polyols, polyether polyols, polyester polyols, and polycarbonate polyols may be mentioned, and any of these may contain a fluorine atom, but (meth) acrylics
  • the polyol preferably contains a fluorine atom
  • the polyether polyol, polyester polyol, and polycarbonate polyol preferably contain no fluorine atom.
  • the polyols (P) may be used alone or in combination of two or more.
  • two or more types of polyols (P) are used in combination, as the combination of polyols (P), from the viewpoint of the extensibility of the multilayer film, among (meth) acrylic polyols, polyether polyols, polyester polyols, and polycarbonate polyols
  • a combination with at least one is preferred, and a combination of (meth) acrylic polyol and polyether polyol or a combination of (meth) acrylic polyol and polycaprolactone polyol is more preferred.
  • a combination of (meth) acrylic polyol and polyether polyol or a combination of (meth) acrylic polyol and polyester polyol is more preferable.
  • Polyisocyanate (I) The polyurethane contained in the surface protective layer is obtained by reacting the above-mentioned polyol (P) with polyisocyanate (I).
  • the polyisocyanate (I) preferably has no aromatic ring in the molecule. According to polyisocyanate (I) having no aromatic ring in the molecule, it is possible to impart excellent weatherability to the surface protective layer. This can reduce yellowing of the surface protective layer over time.
  • polyisocyanate (I) As polyisocyanate (I), a polyisocyanate monomer, a polyisocyanate derivative, etc. are mentioned, for example.
  • polyisocyanate monomers examples include aliphatic polyisocyanates and polyisocyanates having an alicyclic structure.
  • aliphatic polyisocyanate ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatome
  • chill caproate bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.
  • polyisocyanates having an alicyclic structure examples include 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), isophorone diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), 1,3-bis (isocyanatomethyl) Examples include cyclohexane (hydrogenated m-XDI) and the like.
  • polyisocyanate derivative for example, a multimer (for example, dimer, trimer (for example, isocyanurate modified product, iminooxadiazine dione modified product), pentamer, or the like of the polyisocyanate monomer described above, 7 , Etc.), allophanate-modified products (eg, allophanate-modified products produced by reaction of the above-mentioned polyisocyanate monomer with low molecular weight polyol etc.), polyol modified products (eg, polyisocyanate monomer and low molecular weight polyol) Polyol-modified products (alcohol adducts etc.) produced by reaction with a), biuret-modified products (eg biuret-modified products produced by reaction of the above-mentioned polyisocyanate monomer and amines), etc., the above-mentioned polyisocyanates Compounds produced by the reaction of monomers with water, urea-modified products (
  • polyisocyanate (I) may be used alone or in combination of two or more.
  • polyisocyanate (I) Preferably, a polyisocyanate derivative is mentioned, More preferably, the biuret modified body of hexamethylene diisocyanate is mentioned.
  • examples of commercially available biuret-modified hexamethylene diisocyanate include Mitsui Chemicals Co., Ltd. trade name “Takenate (registered trademark) D-165N”.
  • the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the polyisocyanate (I) to the hydroxyl group in the polyol (P) in the monomer serving as the raw material of the polyurethane is preferably 0.8 to 1.2, and 0.9 -1.1 is more preferable.
  • the equivalent ratio (isocyanate group / hydroxyl group) is too low, the scratch resistance of the surface protective layer may be reduced. If the equivalent ratio (isocyanate group / hydroxyl group) is too high, the water resistance of the surface protective layer may be reduced.
  • the equivalent ratio (isocyanate group / hydroxyl group) of isocyanate group in polyisocyanate (I) to hydroxyl group in polyol (P) is obtained by dividing the number of isocyanate groups in polyisocyanate (I) by the number of hydroxyl groups in polyol (P) Ask for.
  • the number of hydroxyl groups in the polyol (P) is calculated based on the following formula.
  • the hydroxyl value is measured according to 4.2 B method of JIS K 1557-1: 2007 (ISO 14900: 2001) “Plastics-Polyurethane raw material polyol test method-Part 1: Determination of hydroxyl value”.
  • the value obtained by Number of hydroxyl groups in the polyol (P) content of the polyol (P) in the raw material monomer (g) x hydroxyl value / 56100
  • the number of isocyanate groups in the polyisocyanate (I) is calculated based on the following formula.
  • the polyurethane contained in the surface protective layer preferably further contains a polythiol (T) unit. That is, the polyurethane is preferably a reaction product of the polyol (P), the polyisocyanate (I) and the polythiol (T).
  • the use of polythiol (T) may improve the scratch resistance of the surface protective layer and the extensibility of the multilayer film in some cases.
  • the polythiol (T) preferably has no aromatic ring in the molecule.
  • the polythiol (T) having no aromatic ring in the molecule can impart excellent weatherability to the surface protective layer. This can reduce yellowing of the surface protective layer over time.
  • the polythiol (T) may have two or more thiol groups in the molecule, and preferably has three or more thiol groups in the molecule.
  • polythiol (T) for example, ethylene glycol dimercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (mercaptopropionate), dipentaerythritol hexakis (3-mercaptoprote) (Pionate), and tris (mercaptopropionyloxyethyl) isocyanurate and the like.
  • trimethylolpropane tris (3-mercaptopropionate) is preferable.
  • the polythiol (T) may be used alone or in combination of two or more.
  • the equivalent weight of the isocyanate group in the polyisocyanate (I) to the hydroxyl group in the polyol (P) and the thiol group in the polythiol (T) in the monomer serving as the polyurethane raw material The ratio [isocyanate group / (hydroxyl group + thiol group)] is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.
  • the equivalent ratio [isocyanate group / (hydroxyl group + thiol group)] is too low, the scratch resistance of the surface protective layer may be reduced.
  • the equivalent ratio [isocyanate group / (hydroxyl group + thiol group)] is too high, the water resistance of the surface protective layer may be reduced.
  • polyisocyanate (I) The equivalent ratio of isocyanate group in polyisocyanate (I) to hydroxyl group in polyol (P) and thiol group in polythiol (T) [isocyanate group / (hydroxyl group + thiol group)] is in polyisocyanate (I) Is determined by dividing the number of isocyanate groups of the above by the total number of hydroxyl groups in the polyol (P) and thiol groups in the polythiol (T).
  • the number of hydroxyl groups in the polyol (P) and the number of isocyanate groups in the polyisocyanate (I) can be determined in the same manner as described above.
  • the multilayer film of the present invention includes a surface protective layer containing the above-described polyurethane.
  • the thickness of the surface protective layer is preferably 1 to 50 ⁇ m, and more preferably 5 to 30 ⁇ m. When the thickness of the surface protective layer is too thin, scratch resistance may be reduced. In addition, when the thickness of the surface protective layer is too thick, appearance defects may occur.
  • the multilayer film of the present invention comprises a substrate layer.
  • the base layer preferably contains at least one of a thermoplastic resin and a thermoplastic elastomer. Thereby, the extensibility of the multilayer film can be improved.
  • thermoplastic resin examples include polyurethane resins, polyolefin resins, polyester resins, polyamide resins, polyvinyl resins, and polycarbonate resins.
  • thermoplastic elastomers polyurethane thermoplastic elastomers, styrene thermoplastic elastomers, acrylic thermoplastic elastomers, polyolefin thermoplastic elastomers, polyvinyl chloride thermoplastic elastomers, polyester thermoplastic elastomers, and polyamide thermoplastic elastomers Etc.
  • the thermoplastic resin or the thermoplastic elastomer may be used alone or in combination of two or more.
  • the base material layer preferably contains a thermoplastic elastomer, and more preferably contains a polyurethane thermoplastic elastomer.
  • the thickness of the base material layer is not particularly limited, and may be 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m.
  • the multilayer film of the present invention includes an adhesive layer laminated and integrated on the second surface of the base material layer.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 10 to 200 ⁇ m, and more preferably 20 to 100 ⁇ m.
  • the adhesive layer contains an adhesive.
  • the pressure-sensitive adhesive is not particularly limited, and, for example, acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, polyurethane-based pressure-sensitive adhesives Pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives and the like are mentioned, and acrylic pressure-sensitive adhesives are preferable.
  • the pressure-sensitive adhesive may be used alone or in combination of two or more.
  • the adhesive layer may contain an additive, if necessary.
  • Additives include, for example, rosin derivative resins, polyterpene resins, petroleum resins, tackifiers such as oil-soluble phenolic resins, plasticizers, fillers, anti-aging agents, antioxidants, pigments such as carbon black, dyes, etc. A coloring agent etc. are mentioned.
  • the pressure-sensitive adhesive may be crosslinked by a general-purpose crosslinking agent such as an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, or an isocyanate-based crosslinking agent.
  • the formation of the adhesive layer is not particularly limited, it is carried out by applying and drying an adhesive composition containing an adhesive and, if necessary, an additive and a crosslinking agent, on the second surface of the base material layer. . An adhesive layer laminated and integrated on the second surface of the base material layer is thereby formed.
  • the multilayer film of the present invention may further include a metallic glitter layer.
  • the multilayer film can exhibit luster by the metallic glitter layer, and the surface of an article such as an automobile can be decorated in a metallic tone.
  • the metallic glitter layer is not particularly limited, but may be disposed on at least one of the first surface and the second surface of the base layer.
  • An anchor coat layer may be further disposed between the metal glittering layer and a layer adjacent to the metal glittering layer, if necessary.
  • the metallic glitter layer is integrally laminated on the first surface of the substrate layer in the multilayer film
  • the metallic glitter layer is preferably included between the substrate layer and the surface protective layer.
  • the multilayer film includes a base material layer, a metal glitter layer laminated and integrated on the first surface of the base material layer through an anchor coat layer as necessary, and the metal glitter layer And a surface protection layer optionally laminated on the first surface via an anchor coat layer.
  • the metallic glitter layer is integrally laminated on the second surface of the substrate layer in the multilayer film
  • the metallic glitter layer is preferably included between the substrate layer and the adhesive layer.
  • the multilayer film includes a base material layer, a metal glitter layer laminated and integrated on the second surface of the base material layer through an anchor coat layer as needed, and the metal glitter layer And an adhesive layer laminated and integrated through an anchor coat layer on the second surface as required.
  • the metallic bright layer preferably contains a metal.
  • the metal include copper, nickel, chromium, titanium, cobalt, molybdenum, zirconium, tungsten, palladium, indium, tin, gold, silver, and aluminum. Among these, indium and aluminum are preferable. These metals may be used alone or in combination of two or more.
  • the thickness of the metallic glitter layer is preferably 1 nm to 100 nm, and more preferably 1.5 nm to 7.5 nm. When the thickness of the metallic glitter layer is too thin, the glitter may be reduced. In addition, when the thickness of the metallic glitter layer is too thick, the metallic glitter layer may become too hard and a crack may occur.
  • a known method such as a metal deposition method is used.
  • a metal vapor deposition method physical vapor deposition (PVD method) such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) can be mentioned.
  • PVD method physical vapor deposition
  • CVD chemical vapor deposition
  • the anchor coat layer is used to improve the adhesion between the metallic glitter layer and the layer adjacent to the metallic glitter layer.
  • the anchor coat layer preferably contains an anchor coat agent.
  • the anchor coating agent include polyester resins, melamine resins, urea resins, urea-melamine resins, urethane resins, acrylic resins, nitrocellulose resins and the like. These anchor coating agents may be used alone or in combination of two or more.
  • the thickness of the anchor coat layer is not particularly limited, and may be 0.01 to 1 ⁇ m.
  • the multilayer film of the present invention is preferably used to protect the surface of articles such as automobiles, vehicles, airplanes, glass, buildings and billboards.
  • the surface of the article can be protected from dirt and scratches, and the appearance can be maintained for a long time.
  • the multilayer film of the present invention is suitably used as an automobile protective film for protecting the surface of an automobile.
  • a multilayer film can be used by being attached and integrated to a painted surface of an automobile via an adhesive layer.
  • the multilayer film even when water adheres to the multilayer film due to rainfall, washing, or the like, the generation of water marks can also be reduced. Therefore, the multilayer film can maintain the surface of the car beautifully for a long time.
  • the two-component curable coating agent of the present invention comprises a main agent containing a polyol (P) having a hydroxyl value of 25 to 380 mg KOH / g and a fluorine atom content of 0.01 to 20% by mass; And a curing agent.
  • the two-component curable coating agent is suitably used for the formation of the surface protective layer contained in the above-mentioned multilayer film.
  • the polyol (P) and the polyisocyanate (I) in the two-component curable coating agent the same as the polyol (P) and the polyisocyanate (I) described above in the surface protective layer can be used, respectively.
  • the equivalent ratio (isocyanate group / the isocyanate group / the hydroxyl group) in the surface protective layer is also the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the polyisocyanate (I) to the hydroxyl group in the polyol (P) in the two-component curable coating agent. It is preferable to make it the same as that of a hydroxyl group.
  • the main agent of the two-component curable coating agent further contains polythiol (T).
  • the polythiol (T) in the main component of the two-component curing type coating agent the same one as the polythiol (T) described above in the surface protective layer can be used.
  • the equivalent ratio [isocyanate group / (hydroxy group + thiol group)] of isocyanate group in polyisocyanate (I) to hydroxyl group in polyol (P) and thiol group in polythiol (T) in two-component curing type coating agent It is also preferable to make it the same as the equivalent ratio [isocyanate group / (hydroxyl group + thiol group)] described above in the surface protective layer.
  • the main component of the two-part curable coating agent preferably contains a curing catalyst.
  • the curing catalyst include organic metal compounds such as dibutyltin oxide, tin 2-ethyl caproate, tin octylate and dibutyltin dilaurate.
  • the curing catalysts may be used alone or in combination of two or more.
  • Additives may be added to the main agent and the curing agent of the two-component curing type coating agent as needed, as long as the physical properties of the two-component curing type coating agent are not impaired.
  • the additive include an antioxidant, a light stabilizer, a heat resistant stabilizer, an antistatic agent, and an antifoaming agent.
  • the main ingredient and curing agent of the two-part curable coating agent may contain a solvent.
  • the solid content concentration of the main agent is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
  • the curing agent of the two-component curing type coating agent contains a solvent, the solid content concentration of the curing agent is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
  • the solvent examples include hydrocarbons such as pentane, hexane, heptane and cyclohexane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate.
  • hydrocarbons such as pentane, hexane, heptane and cyclohexane
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • esters such as ethyl acetate and butyl acetate.
  • the solvents may be used alone or in combination of two or more.
  • the main agent of the two-component curable coating agent is mixed with a curing agent, and the two-component curable coating agent is applied to the base layer. It is preferable to mix the curing agent with the main ingredient of the two-component curable coating immediately before applying the two-component curable coating to the substrate.
  • a base material layer what was mentioned above as a base material layer contained in the multilayer film is used.
  • a coating method by dip coating method, spray coating method, roll coating method, doctor blade method, screen printing method, bar coater, applicator or the like Casting and the like.
  • the two-component curable coating agent applied on the substrate layer is heated and thermally cured.
  • the polyol (P) contained in the main component of the two-component curable coating agent reacts with the polyisocyanate (I) by heating to form a polyurethane, whereby the two-component curable coating agent is cured and the surface protective layer Is formed.
  • the heat curing time of the two-component curable coating agent is preferably 1 to 30 minutes, and more preferably 1 to 10 minutes.
  • the main component of the two-component curable coating agent is mixed with the curing agent, and the two-component curable coating agent is applied to the first surface of the substrate layer to laminate it on the first surface of the substrate layer
  • An integrated surface protection layer can be formed.
  • a two-component curing type coating agent is suitably used for formation of the surface-protection layer contained in the multilayer film mentioned above, it is not limited to this.
  • a surface protection layer can be formed on the surface of an article by directly applying a two-part curable coating to the surface of the article.
  • Such a surface protective layer is laminated and integrated on the surface of the article without an adhesive layer or a base layer.
  • the surface protective layer can also protect the article surface.
  • limit especially as an article, A car, a vehicle, an airplane, glass, a building, a signboard, etc. are mentioned.
  • the method of using the two-component curing type coating agent described above is the same as the method except that the two-component curing type coating agent is applied to the article instead of the base material layer. You can do it.
  • the surface protection layer laminated and integrated on the article surface without interposing the adhesive layer or the base material layer is the same as the surface protection layer contained in the multilayer film described above, the detailed description is omitted here. Do.
  • the present invention it is possible to provide a surface protection layer which is excellent in watermark resistance and scratch resistance. Therefore, the appearance of the surface of the article to which the surface protective layer is applied can be maintained beautifully over a long period of time.
  • the surface protective layer since the water mark resistance is improved without reducing the squeegee slip property, when the multilayer film including the surface protective layer is bonded to the article surface using a squeegee, the surface protective layer The squeegee can be pressed and slid without being caught up. Therefore, it becomes possible to stick and integrate a multilayer film, without generating a crack on the article surface.
  • the multilayer film is flexible and excellent in extensibility, the multilayer film can withstand the tensile force of the squeegee when attaching the multilayer film to the article surface, and the occurrence of cutting in the multilayer film is reduced. It also becomes possible.
  • composition Examples 2 to 18 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, ⁇ -butyl- ⁇ - (3-methacryloxypropyl) polydimethylsiloxane (weight average molecular weight (Mw) 1,000, JNC Co., Ltd.
  • Etanacol registered trademark
  • UM-90 polythiol (T) (Trimethylolpropane tris (3-mercaptopropionate)), dibutyltin dilaurate as a curing catalyst, and methyl isobutyl ketone were supplied to a reaction vessel and mixed to obtain a main agent (solid content: 40% by mass).
  • the (meth) acrylic polyols obtained in Synthesis Examples 1 to 18 were prepared using the (meth) acrylic polyols in such a way that the amounts of each (meth) acrylic polyol shown in Tables 3 and 4 (solid content)
  • the (meth) acrylic polyol solution containing was supplied to the reaction vessel.
  • the amounts of the (meth) acrylic polyol, polyether polyol, polyester polyol, and polycarbonate polyol obtained in Synthesis Examples 1 to 18 in Examples 1 to 18 and Comparative Examples 1 to 3 are shown in Tables 3 and 4, respectively.
  • the fluorine atom content (% by mass) and the hydroxyl value (mgOH / g) are shown in Tables 3 and 4 for each of the polyols (P) contained in the above.
  • composition shown in Tables 3 and 4 is polyisocyanate (I) (biuret modified product of hexamethylene diisocyanate, content of isocyanate group: 23.3%, Takenate D165N manufactured by Mitsui Chemicals, Inc.), and methyl isobutyl ketone, respectively.
  • a curing agent was added to the main agent and mixed, including the amount (in terms of solids content for polyisocyanate (I)).
  • a two-part curable coating agent was obtained. Thereafter, immediately using the two-component curable coating agent, using a bar coater (No.
  • the first surface of the base material layer (sheet containing polyurethane-based thermoplastic elastomer, Esmer URS manufactured by Nippon Matai Co., Ltd.) Applied on top. Thereafter, the applied two-component curing type coating agent is heated at 120 ° C. for 10 minutes to remove the solvent and thermally cure, and a surface protection layer (10 ⁇ m in thickness) integrally laminated on the first surface of the substrate layer Formed.
  • an acrylic adhesive (Halima Chemicals, Inc., Hariaclon 560CH)
  • an isocyanate-based crosslinking agent Tosoh Corp., Coronate (registered trademark) L-45E
  • an adhesive composition was obtained.
  • the pressure-sensitive adhesive composition was immediately applied to the second surface of the substrate layer using a bar coater (No. 24) to obtain a coated film.
  • the coating was heated at 100 ° C. for 3 minutes to remove the solvent.
  • the release paper was laminated on the coating by slowly rolling a roller (weight: 10 kg) around which the release paper was wound on the coating. Thereafter, the coated film was aged at 40 ° C.
  • the “equivalent ratio” described in Tables 3 and 4 is the “isocyanate group in polyisocyanate (I) to the hydroxyl group in polyol (P)” in Examples 1 to 7 and 9 to 18 and Comparative Examples 1 to 3.
  • Equivalent ratio (isocyanate group / hydroxyl group) and for Example 8, “equivalent ratio of isocyanate group in polyisocyanate (I) to hydroxyl group in polyol (P) and thiol group in polythiol (T) [ It means isocyanate group / (hydroxyl group + thiol group)].
  • Tables 3 and 4 show the contact angle after 1 second (also simply referred to as "initial contact angle”), and the rate of change of the contact angle.
  • the "contact angle after 1 second” was scored according to the following evaluation criteria (A)
  • the "rate of change of contact angle” was scored according to the following evaluation criteria (B).
  • the hydrophilicity of the surface protective layer largely contributes to the water mark resistance of the surface protective layer. Therefore, according to the following evaluation criteria, the rate of change of the contact angle was higher in point distribution than the contact angle after 1 second.
  • Evaluation criteria (A): Contact angle after 1 second 1 point: The contact angle after 1 second is 82 ° or more and less than 90 °. The contact angle after 2 points: 1 second is 90 ° or more and less than 98 °. The contact angle after 3 points: 1 second is 98 ° or more and less than 106 °. 4 points: The contact angle after 1 second is 106 ° or more.
  • the glass plate was placed horizontally. After removing the release paper from the adhesive layer of the multilayer film, the multilayer film was placed on the glass plate such that the adhesive layer and the glass plate were in contact with each other. After that, a squeegee (Probig Rubber spatula, manufactured by Mirarede Co., Ltd.,) was manually slid back and forth 10 times on the surface protective layer while applying a load of 0.3 N, thereby counting the number of scratches generated on the surface protective layer. .
  • a squeegee Probig Rubber spatula, manufactured by Mirarede Co., Ltd.
  • the glass plate was placed horizontally. After removing the release paper from the adhesive layer of the multilayer film, the multilayer film was placed on the glass plate such that the adhesive layer and the glass plate were in contact with each other. Thereafter, a multilayer film was laminated on a glass plate by pressing and sliding a squeegee (Probig Rubber spatula, manufactured by Mirarede Co., Ltd.) on the surface protective layer. The resistance when pressing and sliding the squeegee on the surface protective layer was evaluated according to the following criteria. A: There was no feeling of resistance. B: There was a slight resistance. C: There was a feeling of resistance. D: The resistance was strong, and the squeegee did not slide on the surface protective layer.
  • the present invention it is possible to provide a multilayer film having a surface protective layer which is excellent in watermark resistance and scratch resistance, and a two-component curable coating agent for forming the surface protective layer.
  • the surface protective layer the surface of the article can be protected from dirt and scratches, and an excellent appearance can be maintained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Adhesive Tapes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)
PCT/JP2018/013911 2017-08-31 2018-03-30 多層膜及び二液硬化型コーティング剤 WO2019044019A1 (ja)

Priority Applications (6)

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KR1020207002389A KR102555048B1 (ko) 2017-08-31 2018-08-28 다층막 및 2액 경화형 코팅제
PCT/JP2018/031789 WO2019044843A1 (ja) 2017-08-31 2018-08-28 多層膜及び二液硬化型コーティング剤
US16/642,420 US20200254743A1 (en) 2017-08-31 2018-08-28 Multilayer film and two-liquid curable coating agent
CN201880048913.7A CN110945096B (zh) 2017-08-31 2018-08-28 多层膜和双组分固化型涂覆剂
JP2019539540A JP7208903B2 (ja) 2017-08-31 2018-08-28 多層膜及び二液硬化型コーティング剤
TW107130475A TWI791600B (zh) 2017-08-31 2018-08-31 多層膜及雙液硬化型塗布劑

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WO2020105671A1 (ja) * 2018-11-22 2020-05-28 東レ・ファインケミカル株式会社 フッ素含有重合体粒子
WO2022034398A1 (en) * 2020-08-10 2022-02-17 3M Innovative Properties Company Surfacing film

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JP2021098783A (ja) * 2019-12-20 2021-07-01 富士フイルムビジネスイノベーション株式会社 表面保護樹脂部材
JP7447477B2 (ja) * 2019-12-20 2024-03-12 富士フイルムビジネスイノベーション株式会社 表面保護樹脂部材形成用キット、及び表面保護樹脂部材
CN114058098A (zh) * 2020-08-03 2022-02-18 Ａｇｃ株式会社 膜、其制造方法和用途
JP2022136406A (ja) * 2021-03-08 2022-09-21 ハリマ化成株式会社 二液硬化型コーティング剤及び多層膜
KR102439435B1 (ko) * 2022-01-12 2022-09-05 이대우 도막방수재, 그 제조방법 및 이를 이용한 방수시공방법
JP7324380B1 (ja) * 2022-06-28 2023-08-09 日本ペイントマリン株式会社 塗料組成物及び塗膜

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CN110945096A (zh) 2020-03-31
KR20200047519A (ko) 2020-05-07
TWI791600B (zh) 2023-02-11
JPWO2019044843A1 (ja) 2020-10-15
US20200254743A1 (en) 2020-08-13
CN110945096B (zh) 2022-02-22
TW201934340A (zh) 2019-09-01
KR102555048B1 (ko) 2023-07-17
JP7208903B2 (ja) 2023-01-19
WO2019044843A1 (ja) 2019-03-07

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